DE2733050A1 - CATALYST AND ITS USE IN HYDROGENATING TREATMENT OF PETROLEUM RESIDUAL FRACTIONS - Google Patents

Description

description

The invention relates to the demetallizing and desulfurization of petroleum, preferably those containing residual hydrocarbons contain components and have a considerable metal and sulfur content. In particular The invention relates to a demetallization-desulfurization process for lowering the high metal and Sulfur content of petroleum, again preferably those containing residual hydrocarbon components, and to the use of catalysts for the hydrogenating residue treatment which are particularly effective for such purposes.

Petroleum residue fractions, such as the heavy oil fractions obtained from atmospheric and vacuum crude distillation columns, are typically characterized by the fact that they are undesirable as feed materials for most refining processes because of their high metal and sulfur content. The presence of high concentrations of metals and sulfur and their compounds precludes the effective use of such residues as feedstocks for cracking, hydrocracking and coking and limits the extent to which residues can be used as fuel oil. Perhaps the most undesirable property of such feed materials is their high metal content. The main metal impurities are nickel and vanadium, with iron and small amounts of

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copper also occasionally occur. Trace amounts of zinc and sodium are also found in some feed materials. As the vast majority of these metals, when present in crude oil, have very large hydrocarbon molecules are associated, the heavier fractions obtained in the raw distillation contain essentially all of the raw material existing metal, the metals accumulating in particular in the asphaltene residue fraction. The metal impurities are typically large organometallic complexes such as metal porphyrins and metal asphaltenes.

At present, cracking operations are generally carried out with petroleum fractions lighter than the residual fractions. Such cracking is usually carried out in a at a temperature of about 427 to ⁰ 816 C (800 to 1500 ⁰ F), a pressure of about 1 to 5 kg / cm and a weight hourly space velocity of about 1 to 10OO operated reactor. Typical cracking feeds are coke and / or crude gas oils, vacuum tower overheads, etc., with an API density range between about 15 and about 45. Because these cracking feeds are lighter than residual hydrocarbon fractions, residual fractions are characterized by an API value less than about 20, they do not contain substantial proportions of the heavy and large molecules in which metals are enriched.

If metals are present in the feed to a cracking unit, they are deposited on the cracking catalyst. The metal

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Oils act as a catalyst poison and increase performance of the cracking process by changing the catalyst to such an extent that it favors increased hydrogen production will.

The amount of in a given hydrocarbon stream metals present is generally referred to by petroleum experts as referring to the "metal factor" of a feed material judged. This factor is equal to the sum of the metal concentrations in ppm of iron and vanadium plus ten times the amount of nickel and copper in ppm. The factor can be expressed by the following equation:

F _m = Fe + V + 10 (Ni + Cu).

A feed with a metal factor> 2.5 indicates a feed that significantly affects the cracking catalyst Extent will poison. A typical atmospheric Kuwait raw material, generally referred to as average metal content is considered to have a metal factor of about 75 to about 100. Since almost all metals with the Residue fraction of the raw material are combined, it is clear that the removal of metals to 90% and above is required is appropriate to such fractions (with a metal factor of about 150 to 200) for cracking feed materials close.

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Sulfur is also undesirable in a feed material to a process plant. The sulfur leads to corrosion
mechanical system components and difficulties in the treatment of products and exhaust gases. At typical cracking conversion rates, about half of the sulfur fed to the plant is _{converted into H 2} S-GaS, which is then converted from the
Light gas product must be removed, usually by scrubbing with a stream of amine. A large proportion of the remaining sulfur is deposited on the cracking catalyst itself. If the
Catalyst is regenerated, at least some of this sulfur is _{oxidized to SO 2} and / or SO-j gas, which must be removed from the exhaust gas, which is normally released into the atmosphere.

The Conradson Carbon Residue or CCR Number is a measure of the ability of a particular feedstock to produce unwanted coke. The bigger the number
is, the greater is this capacity and / or the amount of coke that is produced in the hydrating treatment or processing of a particular feed material. Thus, lowering the CCR number by reducing coke precursors is a quite desirable advantage of the invention.

Such metal and sulfur impurities present similar hydrocracking problems that are typically carried out with feedstocks that even
are even lighter than those fed to a cracking unit

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are, and therefore typically have even smaller amounts of metals. Hydrocracking catalysts are so sensitive to metal poisoning that a first or preliminary stage to remove the trace metals is often used. Typical hydrocracking reactor conditions consist (400 to 1OOO F) and a pressure of 7 to 246 kg / cm ² gauge (100-3500 psig) at a temperature of 204-538 ⁰ C.

In the past, and to a limited extent still today, high molecular weight feedstocks containing sulfur and metal have often been processed in a coker to effectively remove metals and also some of the sulfur, with the impurities remaining in the solid coke. Coking is typically carried out in a reactor or a drum at about 427-593 ⁰ C (800 to 1100 ° F) and a pressure of 1 to 10 kg / cm, and heavy oils into lighter gas oils, gasoline, gas and solid coke are transferred. However, there are limits to the amount of metal and sulfur that can be tolerated in the product coke if it is to be salable. Thus, there is a significant need to develop both economical and effective means of removing and recovering metal and non-metal contaminants from various petroleum fractions so that the conversion of such contaminated feed materials to more desirable product can be carried out efficiently . Thus , the invention is particularly concerned with lowering Conradson carbon residue and removing metal and sulfur contaminants from

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Hydrocarbon materials contaminated therewith.

U.S. Patent 3,383,301 is concerned with demetallizing and desulfurization using an alumina-based catalyst on which a hydrogenating component is built is. The pore size properties of the catalyst obtained differ considerably from those of the invention Catalyst. Furthermore, the known Ka-'talysator lacks the alkali metal content.

US Pat. No. 3,730,879 is concerned with the desulfurization of crude oil or petroleum residues containing the asphaltene fraction, by selective catalytic hydrogenation under hydrogen partial pressure and using at least one catalyst bed comprising a metal from Group VI and VIII on a support, in which at least 50% (in particular 50-90%) of the total pore radii in the range from 50 to 100 8 (100 to 200 8 Diameter). The catalyst can also contain 0.5 to 2 percent by weight sodium.

Other pertinent patents in this field are: U.S. Patents 2,890,162, 3,242,101, 3,393,148, 3,648 688, 3 714 032 and 3 730 879. However, none of these publications affects the special pore distribution and the alkali metal content, how they distinguish the catalyst according to the invention nen.

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The invention relates to catalysts for hydrogenative demetallization and desulphurisation which contain a hydrogenating component, e.g. cobalt oxide and molybdenum oxide, activated with potassium oxide and together with an aluminum oxide carrier, such a composite catalyst having a surface area of about 80 to about 150 m / g, a total pore volume from about 0.450 to about 0.550 ml / g in pores with a diameter > 30 8, not less than about 25% of this volume in pores with a diameter in the range from about 30 to 100 8, at least about 30% of this volume in pores within of the range from about 100 to 150 8, ie having no less than about 55% of the pore volume in pores with a diameter in the range of about 30 to 150 8, no more than about 2% of this volume in pores with a diameter in the range of 200 to 300 8, not more than about 15% of this pore volume in pores with a diameter Ξ * "3OO 8.

A metal and / or sulfur-containing hydrocarbon feed is charged with a catalyst according to the invention under a hydrogen pressure of about 35 to 211 kg / cm gauge (500 to 300 psig) and a hydrogen circulation rate of about 28.3 to 425 m ³ / barrel (10OO to 15,000 scf / bbl) feed material to a temperature of about 316-454 ⁰ C (600 to 850 ⁰ F) and brought to a liquid hourly space velocity of 0.1 to 5.0 in contact.

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Catalysts having a surface area of about 80 to about 150 m ² / g to work well, the preferred surface is but 135 m / g or less, preferably at a pore volume in pores greater than about 30 8 of about 0.450 to about 0.550 ml / g.

The catalyst according to the invention is impregnated a suitable particulate, refractory base material, e.g., alumina, prepared with the hydrating components; in a preferred embodiment, cobalt oxide and molybdenum oxide activated with an alkali metal are activated brought together a gamma-alumina support. A specific manufacturing method is detailed below. Solid, porous, particulate substances that can also be used successfully in catalysts according to the invention, include relatively large pore silica / alumina or a cf-V alumina support.

As noted above, gamma-alumina is preferred for use in the present invention, and as noted in Alumina Properties, page 46, Newsome, Heiser, Rüssel and Stump (Alcoa Research Laboratories 1960), the gamma-alumina phase can only be fired by firing one of-alumina -Monohydrate form can be achieved directly. Of monohydrate is at about 500 ⁰ C in the gamma phase and crosses the transition point in the <T-phase at about 850 ⁰ C and enters the tJ phase with a narrow temperature range about 1060 ⁰ C. The transition point between v - and c (-phase is around 1150 ⁰ C. It should be noted that so-

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probably β- trihydrate and c ^ -trihydrate aluminum oxides can be converted into the of-monohydrate form.

The feed material to be freed of metal can be any metal and / or sulfur-containing petroleum material, preferably one that contains residue fractions. A procedure according to the working conditions described above is particularly advantageous in connection with feed materials with a metal factor > 25.

The feed material can be a complete raw material, but since the high metal and sulfur containing components of a crude oil are easily enriched in the higher boiling fractions, the process of the invention is more commonly applied to a bottom fraction of a petroleum, ie one which is produced by atmospheric distillation of a crude Petroleum for the removal of lower boiling points such as naphtha and fuel oil, or by vacuum distillation of an atmospheric residue for the removal of gas oil. Typical residues to which the invention is applicable are typically composed of residue hydrocarbons boiling above 482 ^° C (900 ^° F) and contain a significant amount of asphaltic materials. Thus, the feed material may be one which has an initial or 5 -% -, provided the boiling point is slightly below 482 ⁰ C (9OO ⁰ F), that a substantial proportion, for example about 40 or 50 percent by volume, of the hydrocarbon components

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boil above 482 ^° C (900 ^° F). A hydrocarbon material
with a 50% boiling point of about 482 ⁰ C (900 ⁰ F) with a
Asphalt content, 4 weight percent sulfur, and 51 parts per million nickel and vanadium exemplify such feed material. Typical process conditions can
be defined as a feed material containing metal and / or sulfur as an impurity with the catalyst of the invention under a hydrogen pressure of about 35 to

2
211 kg / cm gauge (5OO to 30OO psig), a temperature of 316-454 ⁰ C (600 to 850 ⁰ F) and a liquid hourly space velocity of 0.1 to 5 into contact
is brought.

The hydrogen gas used in hydrative demetallization / desulfurization is ^{dispensed at a rate between about 28.3 and 425 m 3} / barrel (1000 and 15000 scf / bbl) feed and preferably between about 85 and 227 m / barrel (30000 and 8000 scf / bbl ) kept in circulation. The purity of the
Hydrogen can be between 60 and 100%. When the hydrogen is recycled, as is usual, it is desirable to ensure that some of the recycled gas is vented and a supplemental amount of hydrogen is added in order to keep the purity of the hydrogen within the stated range. Usually such diversion measures provide satisfactory removal of hydrogen sulfide from the recycle gas. However, if desired, the recycled gas can be filled with a chemical absorbent for hydrogen sulphide.

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Washed hydrogen or otherwise treated in a known manner to reduce the hydrogen sulfide content before recycling to belittle.

The invention is particularly advantageous where the hydrogenating demetallization / desulfurization without simultaneous cracking of the hydrocarbons present in the feed material he follows. In order to achieve this, the temperature and the air flow velocity within the ranges previously given are chosen to lower the metal content of the feed material from about 75 to 98, preferably over 90% leads.

The hydrogenating component of the catalysts disclosed herein can be any material or combination thereof which has a hydrogenating and desulphurising effect on the feed material under the reaction conditions used. For example are in a hydrogenation reaction when the hydrogenating component is selected from group VIb and a metal from group VIII promoting form and activated by potassium oxide particularly effective catalysts for the purposes of the invention those containing molybdenum oxide and cobalt oxide activated with potassium oxide. Preferred catalysts of this class are consequently those containing the oxides or sulphides of cobalt and molybdenum and activated with potassium oxide, but others Combinations of iron group metals and molybdenum, such as nickel and molybdenum, nickel and tungsten, or other metals of the

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Groups VIb and VIII of the periodic table individually or in combination are also suitable. The hydrogenating components of the catalysts of the invention can be sulfidized or unsulfided form can be used.

If the use of a catalyst in sulfided form is desired, the catalyst can be added after firing or after firing and reduction prior to contact with the feed material by contact with a sulfidation mixture of hydrogen and hydrogen sulfide at a temperature in the range of about 204 to 427 ^° C (400 to 800 ⁰ F) are presulfided at atmospheric pressure or elevated pressures. The presulfiding can conveniently be carried out at the beginning of a cycle period under the same conditions as are to be used at the beginning of such a period. The exact proportions of hydrogen and hydrogen sulfide are not critical and mixtures containing low or high levels are preferred for economic reasons. If the unused hydrogen and hydrogen sulfide that was used for the presulfiding is recycled through the catalyst bed, any water formed during the presulfiding is preferably removed before being recycled through the catalyst bed. It will be understood that elemental sulfur or sulfur compounds, for example mercaptans, or carbon disulfide, which can give hydrogen sulfide under the sulfidation conditions, can be used in place of hydrogen sulfide.

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Although the presulfiding of the catalyst is preferred it is emphasized that this is not essential since the catalyst is normally in a very short time by contact with the highly sulfur-containing feed materials to be used are sulfided under the process conditions disclosed here will.

The catalysts of the invention preferably contain about 2 to about 10 percent by weight cobalt oxide or sulfide, about 5 to about 20 percent by weight molybdenum oxide or sulfide and about 0.1 to about 2.5 percent by weight alkali metal oxide, ie, about 0.1 to about 2.5 Weight percent potassium oxide, for example, has proven advantageous, and even more, preferably about 0.3 to about 1.5 weight percent, by successively impregnating a ό- and / or v-alumina carrier with suitable amounts of, for example, molybdenum oxide and cobalt oxide and then at 538 ⁰ C (1000 ⁰ F) is fired for about 3 to about 10 hours, whereupon it is impregnated with a salt which provides potassium oxide and is burned for about 3 hours at 538 ⁰ C (1000 ⁰ F).

Further advantages, features and embodiments of the invention result from the following description of the examples.

Examples 1 and 2

With these special designs, two catalogs were

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lysatoren (Examples 1 and 2) by impregnating aluminum oxide with cobalt / molybdenum oxides, as described in detail in Example 3, produced; Example 1 is a commercially available one Prototype with cobalt and molybdenum oxides on a porous aluminum oxide support. Example 2 was then made with potassium oxide such as described below in Example 4, impregnated.

These two catalysts were then tested for demetallizing and desulfurizing activities on the shake bomb facility (described below) with atmospheric Lagomedia residue with the results shown in Table I. Thus, Table I illustrates the relative demetallization / desulfurization activity of similar catalysts, one activated with alkali metal oxide and the other not. The working conditions were 399 ⁰ C (750 F), 141 kg / cm ² gauge (2OOO psig), 20 oil / catalyst weight, 80 min. Table II illustrates the effect of different amounts (from about 0.2 to about 2.3 percent by weight) Alkali metal on the catalyst activity, for example of potassium oxide on the demetallization / desulfurization activity of catalysts according to the invention.

The aforementioned shake bomb has been described by Payne et al., "The Shaker Bomb", Industrial and Engineering Chemistry, Vol. 50, No. 147 (1958). Briefly summarized, the shaking bomb is a laboratory tool for the investigation of thermal processes under controlled temperature / time / pressure conditions with an electric motor, a drive with variable

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ler speed, a modified single piston gas engine (20 to 20OO cycles / min), attached to a small replaceable metal bomb, which ^{can be heated from room temperature to the thermal conversion range of 427 to 566 0} C (800 to 1050 ⁰ F) and cooled very quickly, while the contents are vigorously agitated, as well as with temperature and pressure regulating devices and recording devices. Process data of the same kind are obtained from shake bomb tests as from a large-scale test facility.

Example 3

The manufacturing process for the commercial prototype of the demetallization / desulfurization catalyst (Example 1) was as follows:

Approximately 525.0 g of alumina extrudate of 0.794 mm (1/32 ") were fired at a temperature of about 1066 ⁰ C (1950 ⁰ F), whereby the alumina to the alumina particular approximately at the transition point between the o- and the" / Phase. Water was added to about 91.7 g of ammonium molybdate (about 81.0% MoO ₃ ) until a total volume of about 289.0 ml was reached. This ammonium molybdate / water solution was mixed with the alumina, which had been held under vacuum for about half an hour , and it was still gently agitated or rolled under vacuum for about 5 min. The vacuum was released and it was heated to 110 ⁰ C (230 ⁰ F) for about 4 h.

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heated resulting in a weight loss on drying of about 236.9 g. Hasser was added to about 69.4 g of CoCl_ · 6H ₂ O (about 99.0% purity) until a total volume of about 239.0 ml was reached. This aqueous cobalt chloride solution was mixed with the aluminum oxide impregnated with molybdenum in vacuo and placed under vacuum for about half an hour and gently agitated for about 5 minutes while still under vacuum. The vacuum was released and the mixture was heated ^{to 110 °} C. (230 ^{° F.) for about 10 h.} Finally, aluminum oxide impregnated with CoO, MoO _{3 was} ^{slowly heated to about 538 °} C. (1000 ^° F.) at about 1.1 ^° C. (2 ^° F.) / min and ^{held at 538 °} C. for about 10 h.

Example 4

The manufacturing process for a catalyst according to the invention (Example 2) was as follows:

A catalyst as defined in Example 3 was prepared, and then 25 g was impregnated to initial moisture with 13 ml of a solution containing 0.73 g of potassium carbonate and ^{calcined in a stream of air at 538 °} C. (1000 ^° F) for about 3 hours, which was led to the deposition of 1.5 weight percent potassium oxide on the catalyst support.

As previously mentioned, the results of the catalyst studies are of Examples 1 and 2 for demetallization / desulfurization activity shown in Table I. With the catalyst disclosed herein with alkali metal oxide, i.e. potassium oxide

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(Example 2) 12.4 weight percent more sulfur was removed than with the commercially available prototype catalyst (Example 1) without the addition of alkali metal oxide. Next formed the catalyst without the alkali metal oxide (Example 1) 11.5 percent by weight more coke on the catalyst.

Example 5

A mixture of 7000 g of CATAPAL SB aluminum oxide (commercially available), a high purity oC alumina monohydrate from an alcohol process, and 4588 g of water were extruded into pellets 0.794 mm (1/32 ") in diameter using a screw press, which were pressed overnight at 121 ⁰ C (25O ⁰ F) in pans h (900 ⁰ F) were baked at 482 ⁰ C and dried in beds with an air flow. 4

A portion of the above product was also heated to 704 ⁰ C (1300 ° F) for 4 hours; 1870 g of this material was impregnated to initial wetness with 1290 ml of solution containing 262.5 g of ammonium molybdate (81.7% MoO ₃ ). The product was ^{dried overnight at 121 °} C. (250 ^° F.), 649 g of volatile material were lost in the process. The product was then impregnated with 649 g of a solution which contained 294 g of cobalt (II) nitrate crystals, ^{dried overnight at 121 °} C. (250 ^° F.) and ^{calcined at 538 °} C. (1000 ^° F.) for 6 h.

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Examples 6 to 10

A number of the catalysts of the invention were prepared by the following procedure, except that the potassium carbonate solutions were of such concentration that 0.2, 0.4, 0.8, 1.5 and 2.3 weight percent potassium oxide on the catalysts after Burning were deposited. 50 g of the catalyst of Example 5 were impregnated with 27 ml potassium carbonate solution (250 F ⁰⁾ overnight (F 1OOO ⁰⁾ baked at 121 ⁰ C and 3 h at 538 ⁰ C in an air stream through the catalyst bed.

The results of the shake bomb test with these catalysts and those of Example 5 are shown in Table II. The results given therein show that the catalysts remove more sulfur with 0.4, 0.8 and 1.5 percent by weight of potassium oxide than a catalyst as in the example 5 is indicated. The results also show that the catalysts with 0.2, 0.4, 0.8 and 1.5 percent by weight of potassium oxide added provide a liquid product with lower CCR values than the catalyst of Example 5. So support the data It is clear in Tables I and II that the catalysts previously described according to the invention have superior desulfurization activity and provide a reduced CCR product lead to reduced coke formation on the catalyst in the hydrogenation treatment and thereby a high demetallization activity keep.

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The aforementioned CCR content is an NaB for the amount of coke that is expected to form in a typical FCC cracking operation. It is determined as follows t

Carbon residue from petroleum products

(Conradson Carbon Residue) ASTM designation D189

Method;

A 10 g sample of the oil is weighed into a tared # O porcelain dish and into a Skidmore iron dish brought, which is provided with a flanged, ventilated lid. This in turn is placed in a sand bath and covered and placed in an insulated holder on a tripod. A sheet metal hood with a chimney on top is used placed over the entire apparatus and supplied with heat from a gas flame. A preheating time of 10 minutes, a burning time of 13 minutes and a final heating time of 7 minutes is required, after which the heating is stopped «Tritt no more smoke appears, the hood and lid are removed, and the bowl is cooled in a desiccator and weighed. The weight percent residue in the bowl or crucible is called Conradson carbon residue (CCR) «For Heavy oils and for light distillates is a slightly modified one Working method required.

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Table I.

Properties and activities of catalysts for the hydrotreatment of residues

catalyst

description size

example

Largo-

Feed atmospheric material: residue

0.794 mn (1/32 ")

R ₂ O addition,% by weight properties Surface area, ^m2 / g 112 Pore volume,

an3 / g> 30 8, 0.455

Pore size distribution

ment,% of total

Pore volume (according to

CoCMoO ₃ / Al ₂ O ₃ S

0.794 rm ^{Ni + V} (1/32 ")

1.5

2-2.5 wt% 195-205 ppm

0.443

Forum acronym υ
8th) η 1.3 2.3 30-50 2.6 3.8 50-80 10.8 17.8 80-100 38.7 41.5 100-15O 30.3 18.9 150-200 1.8 0.45 200-300 14.5 15.1 3OCH- 37.0
64.1 41.6
63.8 activity
% S removal
% V distance

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Table II Influence of ^ O aixf the OoMcAl-O ^ catalyst properties

catalyst

K ₂ O addition,% by weight

Shaking basin results V removal,% S removal,% CCR content,% C on catalyst,% by weight

Catalyst properties

2 surface, m / g

Pore volume cm / g (30 + Ä diameter)

Examples

3 4th 5 6th 7th 8th 0.0 0.2 0.4 0.8 1.5 2.3 64 64 64 62 62 66 44 44 45 47 46 42 5.2 3.5 4.2 4.4 3.7 5.4 10.9 10.9 11.0 9.9 9.9 9.6 139 0.508

Pore size distribution % of the total pore volume _ (according to pore diameter in 8)

30-100 100-150 150-200 200-300 300+

25.8 41.5 16.9 1 »6

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Claims (10)

Dr. D.Thomsen PATE NTANWALTS OFFICE O Tele.on (089) 530211 ** 530212 W. WeinkaUff telegram address I "" Cable address J ^^ Telex 524303 xpert d PATENT LAWYERS MOndMn: Frankfurt / M .: Dr. rer. nat. D. Thomson Dipl.-Ing. W. Weinkauff (Fox Horil 71) Dracdnar Bank AQ. MOnchwi, account 9574237 8000 Manchen 2 Kateer-Ludwig-Piatze July 21, 1977 Mobil Oil Corporation
New York, NY, USA Catalyst and its use in the hydrogenation treatment of petroleum residue fractions Claims 1 / catalyst for the hydrogenation treatment of petroleum residues, characterized in that it contains the oxides and / or sulfides of a metal of group VIb and a metal of 809807/0558 Group VIII contains on an alumina support and with up to 2.5 percent by weight of alkali metal oxide is activated, not less than 25% of the volume of its pores has a pore diameter in the range from 30 to 100 8, not more than 15% of the volume of its pores have a pore diameter over 300 8 and pores over 30 8 in diameter 0.450 make up to 0.550 cm / g of the catalyst. 2. Catalyst according to claim 1, characterized in that it contains 5 to 20 percent by weight of molybdenum oxide and 2 to 10 percent by weight Contains cobalt oxide and 0.1 to 2.5 percent by weight potassium oxide as an activator. 3. Catalyst according to claim 1 or 2, characterized in that that it contains the sulphides of molybdenum and cobalt. 4. Catalyst according to one of claims 1 to 3, the pore volume of which is at least 30% of pores with a diameter in the range from 100 to 150 8 and at least 15% consists of pores with a diameter in the range from 150 to 2OO 8. 5. Catalyst according to one of claims 1 to 4, characterized in that it has a surface area of 80 to 150 m ² / g. 6. Catalyst according to one of claims 1 to 5, characterized 809807/0558 characterized in that the alumina support comprises Γ-, <f- and / or (theta) V-alumina. 7. Use of the catalyst according to one of the claims 1 to 6 in a process for the catalytic hydrogenation treatment of a metal and sulfur impurities Petroleum residue, in which the Ul with hydrogen under conditions of hydrating demetallization / desulfurization • is brought into contact. 8. Use of the catalyst according to claim 7 in one Method which is carried out at a hydrogen pressure of 35 to 211 kg / cm gauge (500 to 3ooo psig), a temperature of 316-454 ⁰ C (6OO to 850 ⁰ F) and a liquid hourly space flow rate of 0.1 to fifth 9. Use of the catalyst according to claim 7 or 8 in a process which is carried out at a hydrogen pressure of 141 to ο
211 kg / cm gauge (2OOO to 3ooo psig), a temperature of 385-454 ⁰ C is performed (725-850 ⁰ F) and a liquid hourly space flow rate of 0.10 to 1.5. 10. Use of the catalyst according to any one of claims 7 to 9 in a process in which the Conradson carboron residue is reduced. 809807/0558